Identification of the Active Sites on Metallic MoO2−xNano‐Sea‐Urchin for Atmospheric CO2Photoreduction Under UV, Visible, and Near‐Infrared Light Illumination

We report an oxygen vacancy (V_o )-rich metallic MoO_2-x nano-sea-urchin with partially occupied band, which exhibits super CO₂ (even directly from the air) photoreduction performance under UV, visible and near-infrared (NIR) light illumination. The V_o -rich MoO_2-x nano-sea-urchin displays a CH₄ evolution rate of 12.2 and 5.8 μmol g_catalyst ^-1 h^-1 under full spectrum and NIR light illumination in concentrated CO₂ , which is ca. 7- and 10-fold higher than the V_o -poor MoO_2-x , respectively. More interestingly, the as-developed V_o -rich MoO_2-x nano-sea-urchin can even reduce CO₂ directly from the air with a CO evolution rate of 6.5 μmol g_catalyst ^-1 h^-1 under NIR light illumination. Experiments together with theoretical calculations demonstrate that the oxygen vacancy in MoO_2-x can facilitate CO₂ adsorption/activation to generate *COOH as well as the subsequent protonation of *CO towards the formation of CH₄ because of the formation of a highly stable Mo-C-O-Mo intermediate.